CN101531770A - Preparation and application of open-cell foamed polyolefin - Google Patents
Preparation and application of open-cell foamed polyolefin Download PDFInfo
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- CN101531770A CN101531770A CN200810037461A CN200810037461A CN101531770A CN 101531770 A CN101531770 A CN 101531770A CN 200810037461 A CN200810037461 A CN 200810037461A CN 200810037461 A CN200810037461 A CN 200810037461A CN 101531770 A CN101531770 A CN 101531770A
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Abstract
The invention relates to a preparation method of open-cell foamed polyolefin. The preparation method comprises the following steps of: mixing the polyolefin with nucleating agent master batch prepared by same olefin type polyolefin granules, a nucleating agent, a foaming-assisting anti-shrinking agent and an antioxidant, putting the obtained mixture into a single-screw or double-screw extruder with the length-diameter ratio of 20-50 for heating, plasticizing and melting, injecting high-pressure gas, fully melting, mixing and extruding out the high-pressure gas and the polyolefin, releasing, expanding, foaming when extruding the obtained mixture out of a mold at an outlet mold of the extruder so as to prepare open-cell foaming products with various shapes. The open-cell foamed products are used as adsorption substrates and adsorption carriers, and can also be used as sound-insulating, sound-absorbing, and heat-insulating materials. According to the strength and visco-elasticity of the polyolefin melt, the invention selects an appropriate position to inject the high-pressure gas, and adjusts the structure of the screw, gas pressure and gas quantity, and the heating temperature so as to lead the polyolefin to be fully foamed and cells to be opened thereon when the materials are extruded out of the outlet mold of the extruder, therefore, the gas among the cells is mutually communicated, thus having relatively high adsorption capacity, overcoming the shortage of difficult cell-opening in the existing polyolefin foaming technology and causing the polyolefin application to be more diversified and practical.
Description
Technical field
The present invention relates to the preparation and the practical application of open-cell foamed polyolefin plastics, relate in particular to the foam preparation method and the use field of pellet, sheet material, tubing and the various profiles of polyolefine hole-opening foaming.
Background technology
Closed pore polyalkene foaming production technology comparative maturity, and use range is quite extensive.But because do not connect mutually between closed pore expanded polyolefin hole, absorption property is very poor, so its application is restricted.Though and open-cell foamed polyolefin also has very big demand, but its hole-opening foaming technology is owing to have certain degree of difficulty on foam process and formulating of recipe, particularly on foam process, reach the higher percentage of open area of foam, screw-rod structure, mold shape, processing temperature, injected gas volume, gas injection pressure all have very significant effects to the percentage of open area of foam, and technical difficulty is bigger.The present invention is according to polyolefine closed pore foaming technique, component design and foaming forming technique voluntarily on this technical foundation, adopt physical foaming technology, be used in combination frothing aid, development and production go out to have the polyolefine hole-opening foaming material of higher hole-opening foaming rate and liquid adsorption rate.
Summary of the invention
The present invention is by special material formulation and foaming complete processing, make polyolefine in the twin screw or single screw extruder of specific length-to-diameter ratio, the horse back release of pressure makes fused polyolefin fully expanded foamed when mixing afterwards by the extruding dies discharging by the injection high pressure gas in complete plastifying fusion process.Emphasis of the present invention is how to make the polyolefine fast foaming under the certain temperature certain pressure, and opens wide perforation mutually between abscess, and typing back foam remains unchanged.
One of purpose of the present invention is carrier or the adsorption substrates of product of the present invention as a kind of adsorptive liquid additive, quick adsorptive liquid additive, be applied to produce and life in the direct annex solution body additives or directly add liquid brings influence to production occasion of inconvenience.Two of the object of the invention is owing to gang up mutually between product abscess of the present invention, specific surface area is big, the adsorption rate height, adsorptive liquid and Powdered additive, as oxidation inhibitor, static inhibitor, linking agent, fire retardant, perfume compound, medicine, auxiliary agent or medicines such as active substance, greatly make things convenient for production application and actually operating, the even adding and the metering that guarantee additive are accurate, need to add weight ratio seldom in being particularly useful for producing, but act on very big liquid, it is inhomogeneous that directly interpolation may cause interpolation, and the best way is to be dispersed in the body after adopting the bulk resin of same substrate to make the prior adsorptive liquid of hole-opening foaming material again, avoids the generation of ununiformity; Or the annex solution scale of construction is more, and it is fashionable that liquid is difficult for being influenced its processing space by the material rapid absorption, can adopt the part bulk material to make the hole-opening foaming body after, add again behind the preadsorption liquid, guarantee to add metering accurately; Open-cell foamed polyolefin is made the goods of different shape moulding in the daily life in addition, be used to adsorb liquid such as perfume compound or insecticide after, allow it slowly discharge fragrance or deinsectization medicine, reach deodorizing of long-acting release fragrance and anthelmintic purpose.Three of purpose of the present invention is in the sewage treatment process because expanded polyolefin light weight of the present invention, swim on the water surface, because the perforate adsorption function of itself is strong,, reach the purpose of rapid decontamination decontamination again so can adsorb the greasy dirt that swims in the sewage surface fast.Four of purpose of the present invention is because product foaming degree of the present invention is very high, and runs through mutually between abscess, so can be used as the sound-absorbing sound and thermal insulating material again.
The present invention is achieved in that
This absorption preparation method of open-cell foamed polyolefin, it is characterized in that: with polyolefin pellets and polyolefin pellets by identical olefines, nucleator, help the foaming antishrinking agent, the nucleator masterbatch that oxidation inhibitor is made drops into twin screw or single screw extrusion machine behind the uniform mixing in proportion, in forcing machine heating and melting extrusion, inject high pressure gas, and make their thorough mixing even, the polyolefine molten mass that contains high pressure gas when screw rod is extruded under the effect at the outlet of extruder mould at once release of pressure expand and make the hole-opening foaming pellet or the goods of different shape, polyolefin pellets and nucleator masterbatch weight ratio are 100:0.5～8.
Open-cell foamed polyolefin among the present invention comprises in the composition of parts by weight:
Polyolefine 100
Nucleator masterbatch 0.5～8;
Wherein nucleator masterbatch comprises in the composition of parts by weight:
Identical olefines polyolefine 15～30
Nucleator 40～70
Help foaming antishrinking agent 3～10
Oxidation inhibitor 2～8.
Polyolefine among the present invention is a polyethylene, polypropylene, ethylene vinyl acetate, ethylene methyl acrylate copolymer, ethylene ethyl acrylate copolymer, the ethylene butyl acrylate multipolymer, polystyrene styrene ethylene butadienecopolymer, styrene-butadiene-copolymer, maleic anhydride grafted polyethylene, maleic anhydride inoculated polypropylene, the maleic anhydride grafted ethene vinyl acetate between to for plastic, silane grafted polyethylene, silane grafted polyacrylate, silane grafted ethene vinyl acetate between to for plastic is chosen any one kind of them or the blend of several resins.
Nucleator among the present invention is aluminium hydroxide, magnesium hydroxide, organophosphate salt, 2,2 '-methylene radical-two (4, the 6-di-tert-butyl-phenyl) chooses any one kind of them in sodium sulfovinate, diphenylmethylene sorbyl alcohol, two Asias (to methyl) benzyl Sorbitol Powder, talcum powder, Magnesium Silicate q-agent, lime carbonate, silicon-dioxide, white carbon black, the quartz sand or several, its effect is to form nucleus, blow point when becoming foaming makes foaming closely evenly.
Among the present invention to help the foaming antishrinking agent be to choose any one kind of them in stearic acid, oleic acid, Tripolyglycerol monostearates, stearic acid monoglycerides, polyglycerol ester acid esters, polyglycerol monoesters, the stearic acid list double glyceride or several, its effect is to play the opposing foam to shrink in foaming process.
Oxidation inhibitor among the present invention is that four [3-(3 '; 5 ';-di-t-butyl-4 '-hydroxy phenyl) propionic acid] pentaerythritol ester; β-(4-hydroxyl-3; the 5-di-tert-butyl-phenyl) the positive octadecanol ester of propionic acid; tricresyl phosphite (nonyl phenyl ester); tricresyl phosphite (2; 4 di-tert-butyl-phenyls) ester; Tyox B; 4; 4 '-thiobis (the 6-tertiary butyl-3-methylphenol); 4; 4 '-thiobis (6-tertiary butyl meta-cresol); 1; 1; 3-three (2-methyl-4-hydroxyl-5-tert-butyl-phenyl) butane 2; the 6-DI-tert-butylphenol compounds; 2; 6-di-tert-butyl-4-methy phenol or 4-methylol-2; choose any one kind of them in the 6-DI-tert-butylphenol compounds or several, its effect is the protection polyolefine, improves the stability that polyolefine is heated.Avoid polyolefine to be subjected in the thermal process and strong oxidizing substance effect such as oxygen, oxidation takes place and polyolefine is degraded.
The preparation method one of the nucleator masterbatch among the present invention: will be with polyolefin pellets, the nucleator of the identical olefines of open-cell foamed polyolefin, help foaming antishrinking agent, oxidation inhibitor thorough mixing in high-speed mixer in proportion, compound is put into the single screw extrusion machine extruding pelletization of processing 120 ℃-180 ℃ of extrusion temperatures, and granulation can adopt air-cooled tie rod pelletizing and air-cooled flour milling pelletizing to choose any one kind of them; The preparation method two: will be with polyolefin pellets, the nucleator of the identical olefines of open-cell foamed polyolefin, to help foaming antishrinking agent, oxidation inhibitor directly to put into temperature by a certain percentage be to mix plasticizing in 120 ℃-180 ℃ the Banbury mixer, enter the forcing machine granulation after the plasticizing, 120 ℃-180 ℃ of extruder temperatures, granulation can adopt air-cooled pelletizing of tie rod and air-cooled flour milling pelletizing to choose any one kind of them.
The twin screw extruder that the preparation open-cell foamed polyolefin is selected for use among the present invention and the length-to-diameter ratio of single screw rod are between the 20-50, gas injection port is set in the charging opening 1/3-2/3 place of screw rod later on, gas injection valve diameter 0.1mm-1.0mm, injecting gas pressure 0.5MPa-50MPa, adopt topping-up pump to help supercharging in case of necessity, the body temperature of forcing machine is set between 80 ℃-200 ℃ from charging opening to machine neck, and head temperature is set in 100 ℃-160 ℃.
High pressure gas among the present invention are to choose any one kind of them in air, carbonic acid gas, nitrogen, methane, monochloro methane, methylene dichloride, Trichloromonofluoromethane, Refrigerant 12, ethane, propane, butane, the rare gas element.
When the various open-cell foamed polyolefin goods that product of the present invention is made are applied in the plastic working to add liquid as the carrier and the adsorption substrates of adsorptive liquid, the carrier that adsorbs long-acting release after printing ink, the perfume fragrance drug absorption in the sewage treatment process in the greasy dirt of absorption in the sewage, the ink paste seal, and as the sound insulating and absorbing lagging material.
Embodiment
In conjunction with the embodiments content of the present invention is described further, the composition in following examples is weight part.
One, polyethylene hole-opening foaming
Nucleator masterbatch is formed
| Polyvinyl resin | 21 |
| Nucleator | 65 |
| Blowing promotor | 8 |
| Oxidation inhibitor | 6 |
The hole-opening foaming polyethylene is formed
| Embodiment 1 | Embodiment 2 | |
| Polyvinyl resin | 100 | 100 |
| Nucleator masterbatch | 2 | 5 |
At first with nucleator, help foaming antishrinking agent and oxidation inhibitor to put into internal mixing and plasticizing in 160 ℃ the Banbury mixer by said ratio, enter extrusion temperature after the plasticizing and be in 160-180 ℃ the single screw extrusion machine, adopt the air-cooled mode of flour milling to cause master batch.
Poly melting index among the embodiment 1 is 2.0g/10min, nucleator master batch and polyethylene are put into the single screw extrusion machine extrusion foaming by the proportioning mixing, single screw extrusion machine length-to-diameter ratio 36, gas injection port is set between fluxing zone and the metering zone, air injection opening diameter 0.2mm, high pressure gas are carbonic acid gas, and gas injection pressure is 30MPa, adopt topping-up pump to help supercharging.
The extrusion foaming technological temperature of single screw rod ℃:
| Feeding section | Fluxing zone | Metering zone | The machine neck | Head |
| 140～160 | 160～180 | 160～180 | 140～170 | 120～160 |
The polyethylene foam adsorption rate of making by above-mentioned technology and prescription is 〉=50%, adsorbs a large amount of liquid flame retardants when being used to process flame-proof polyethylene.
Poly melting index among the embodiment 2 is 6.0g/10min, nucleator master batch and polyethylene are put into the twin screw extruder extrusion foaming by the proportioning mixing, twin screw extruder length-to-diameter ratio 40, gas injection port is set in the metering zone middle part, gas injection valve diameter 0.6mm, high pressure gas are nitrogen, and gas injection pressure is 20MPa.
The extrusion foaming technological temperature of twin screw ℃:
| Feeding section | Fluxing zone | Metering zone | The machine neck | Head |
| 130～150 | 160～180 | 180～200 | 160～180 | 140-160 |
The polyethylene foam adsorption rate of making by above-mentioned technology and prescription is 〉=50%, makes the artwork of different shape, is used to adsorb perfume.
Two, ethylene vinyl acetate hole-opening foaming
Nucleator masterbatch is formed
| Ethylene-vinyl acetate | 18 |
| Nucleator | 60 |
| Blowing promotor | 10 |
| Oxidation inhibitor | 5 |
The hole-opening foaming ethylene vinyl acetate is formed
| Embodiment 3 | Embodiment 4 | |
| Ethylene vinyl acetate | 100 | 100 |
| Nucleator masterbatch | 3 | 5 |
Nucleator, blowing promotor and oxidation inhibitor put into internal mixing and plasticizing in 110 ℃ the Banbury mixer by said ratio, enter extrusion temperature after the plasticizing and be in 60-140 ℃ the single screw extrusion machine, adopt the air-cooled mode of flour milling to cause master batch.
The vinyl acetate content of the ethylene vinyl acetate among the embodiment 3 is 14%, nucleator master batch and ethylene-vinyl acetate copolymer resins are put into the single screw extrusion machine extrusion foaming by the proportioning mixing, the length-to-diameter ratio of single screw extrusion machine is 36, gas injection port is set between fluxing zone and the metering zone, air injection opening diameter 0.3mm, high pressure gas are nitrogen, and gas injection pressure is 17MPa.
The extrusion foaming technological temperature of single screw rod ℃:
| Feeding section | Fluxing zone | Metering zone | The machine neck | Head |
| 60～70 | 90～100 | 120～140 | 120～130 | 110-120 |
The ethylene vinyl acetate foaming product of making by above-mentioned technology and prescription adsorbs the greasy dirt on sewage surface.
The vinyl acetate content of ethylene vinyl acetate is 28% among the embodiment 4, nucleator master batch and ethylene-vinyl acetate copolymer resins are put into the twin screw extruder extrusion foaming by the proportioning mixing, the length-to-diameter ratio of twin screw extruder is 40, gas injection port is set in the metering zone middle part, gas injection valve diameter 0.4mm, high pressure gas are nitrogen, and gas injection pressure is 30MPa, adopt topping-up pump to help supercharging.
The extrusion foaming technological temperature of twin screw ℃:
| Feeding section | Fluxing zone | Metering zone | The machine neck | Head |
| 60～70 | 90～100 | 120～140 | 120～130 | 100-120 |
The foaming ethylene vinyl acetate of making by above-mentioned technology and prescription is used as the sound insulating and absorbing decorative sheet.
Claims (10)
1. preparation method of open-cell foamed polyolefin, it is characterized in that: with polyolefin pellets with by identical olefines polyolefin pellets, nucleator, help the foaming antishrinking agent, the nucleator masterbatch that oxidation inhibitor is made drops into twin screw or single screw extrusion machine behind the uniform mixing in proportion, in forcing machine heating and melting extrusion, inject high pressure gas, and make their thorough mixing even, release of pressure expanded when the polyolefine molten mass that contains high pressure gas was extruded under the effect outlet mould at screw rod, make the hole-opening foaming pellet or the goods of different shape, polyolefin pellets and nucleator masterbatch weight ratio are 100:0.5～8.
2. method according to claim 1 is characterized in that: described open-cell foamed polyolefin comprises in the composition of parts by weight:
Polyolefine 100
Nucleator masterbatch 0.5～8;
Wherein nucleator masterbatch comprises in the composition of parts by weight:
Identical olefines polyolefine 15～30
Nucleator 40～70
Help foaming antishrinking agent 3～10
Oxidation inhibitor 2～8.
3. method according to claim 1 and 2 is characterized in that: described polyolefine is a polyethylene, polypropylene, ethylene vinyl acetate, ethylene methyl acrylate copolymer, ethylene ethyl acrylate copolymer, the ethylene butyl acrylate multipolymer, polystyrene, the styrene ethylene butadienecopolymer, styrene-butadiene-copolymer, maleic anhydride grafted polyethylene, maleic anhydride inoculated polypropylene, the maleic anhydride grafted ethene vinyl acetate between to for plastic, silane grafted polyethylene, silane grafted polyacrylate, choose any one kind of them in the silane grafted ethene vinyl acetate between to for plastic or the blend of several resins.
4. method according to claim 1 and 2, it is characterized in that: described nucleator is aluminium hydroxide, magnesium hydroxide, organophosphate salt, 2, choose any one kind of them in 2 '-methylene radical-two (4, the 6-di-tert-butyl-phenyl) sodium sulfovinate, diphenylmethylene sorbyl alcohol, two Asias (to methyl) benzyl Sorbitol Powder, talcum powder, Magnesium Silicate q-agent, lime carbonate, silicon-dioxide, white carbon black, the quartz sand or several.
5. method according to claim 1 and 2 is characterized in that: described to help the foaming antishrinking agent be to choose any one kind of them in stearic acid, oleic acid, Tripolyglycerol monostearates, stearic acid monoglycerides, polyglycerol ester acid esters, polyglycerol monoesters, the stearic acid list double glyceride or several.
6. method according to claim 1 and 2, it is characterized in that: described oxidation inhibitor is that four [3-(3 ', 5 ',-di-t-butyl-4 '-hydroxy phenyl) propionic acid] pentaerythritol ester, β-(4-hydroxyl-3, the 5-di-tert-butyl-phenyl) the positive octadecanol ester of propionic acid, tricresyl phosphite (nonyl phenyl ester), tricresyl phosphite (2,4 di-tert-butyl-phenyls) ester, Tyox B, 4,4 '-thiobis (the 6-tertiary butyl-3-methylphenol), 4,4 '-thiobis (6-tertiary butyl meta-cresol), 1,1,3-three (2-methyl-4-hydroxyl-5-tert-butyl-phenyl) butane 2, the 6-DI-tert-butylphenol compounds, 2,6-di-tert-butyl-4-methy phenol or 4-methylol-2,6 di t butyl phenol, in choose any one kind of them or several.
7. method according to claim 1 and 2, it is characterized in that by identical olefines polyolefin pellets, nucleator, help foaming antishrinking agent, oxidation inhibitor to make the preparation method one of nucleator masterbatch: with identical olefines polyolefin pellets, nucleator, help foaming antishrinking agent, oxidation inhibitor thorough mixing in high-speed mixer by a certain percentage, compound is put into the single screw extrusion machine extruding pelletization of processing 80 ℃-180 ℃ of extrusion temperatures, and granulation can be adopted in air-cooled tie rod pelletizing and the air-cooled flour milling pelletizing any; The preparation method two: with identical olefines polyolefin pellets, nucleator, to help foaming antishrinking agent, oxidation inhibitor directly to put into temperature by a certain percentage be that 80 ℃-180 ℃ Banbury mixer mixes plasticizing, enter the forcing machine granulation after the plasticizing, 80 ℃-180 ℃ of extruder temperatures, granulation can be adopted in air-cooled tie rod pelletizing and the air-cooled flour milling pelletizing any.
8. method according to claim 1 and 2, it is characterized in that any of described twin screw extruder that is used for preparing open-cell foamed polyolefin and single screw extrusion machine, its length-to-diameter ratio is between the 25-50, gas injection port is set in the charging opening 1/3-2/3 place of screw rod later on, diameter 0.1mm-the 1.0mm of gas injection valve, injecting gas pressure 0.5MPa-50MPa, adopt topping-up pump to help supercharging in case of necessity, the body temperature of forcing machine is set in 80 ℃-200 ℃ from charging opening to machine neck, and head temperature is set in 100 ℃-160 ℃.
9. method according to claim 1 and 2 is characterized in that: described high pressure gas are to choose any one kind of them in air, carbonic acid gas, nitrogen, methane, monochloro methane, methylene dichloride, Trichloromonofluoromethane, Refrigerant 12, ethane, propane, butane, the rare gas element.
10. the application of the described open-cell foamed polyolefin of claim 1, it is characterized in that: described open-cell foamed polyolefin is used for plastic working when adding liquid or liquid-solid mixed additive as the carrier and the adsorption substrates of adsorptive liquid, the carrier that adsorbs long-acting release after printing ink, the perfume fragrance drug absorption in the sewage treatment process in the greasy dirt of absorption in the sewage, the ink paste seal, and as the sound insulating and absorbing lagging material.
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